Regiodivergent reductive coupling of 2-substituted dienes to formaldehyde employing ruthenium or nickel catalyst: hydrohydroxymethylation via transfer hydrogenationElectronic supplementary information (ESI) available: Experimental procedures and spectroscopic data for all new compounds (1H NMR, 13C NMR, IR, HRMS) including images of NMR spectra. See DOI: 10.1039/c3sc22051f

• Main Authors: Köpfer, Alexander, Sam, Brannon, Breit, Bernhard, Krische, Michael J
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c3sc22051f

The regioselective reductive coupling of paraformaldehyde to 2-substituted dienes at positions C1, C2 and C3 was achieved using metal catalysts based on nickel, cationic ruthenium and neutral ruthenium, respectively. Whilst C1 adducts predominate using dienes, silicon- or tin-substituted dienes exhibit C4 regioselectivity - the first time that this regioselectivity has been observed for the coupling of 2-substituted butadienes to aldehydes. Both nickel- and ruthenium-catalyzed processes avoid pyrophoric or mass intensive reducing agents, using paraformaldehyde or isopropanol, respectively. These couplings may be viewed as alternatives to diene hydroformylation, for which regioselective formation of constitutionally isomeric products has not yet been achieved. As an alternative to hydroformylation, we report the regioselective reductive coupling of paraformaldehyde to all four positions of 2-substituted butadienes to form homoallylic or bishomoallylic alcohols employing nickel or ruthenium catalysts.